Electrical multilayer lamination transfer films

ABSTRACT

Transfer films, articles made therewith, and methods of making and using transfer films to form an electrical stack are disclosed. The transfer films ( 100 ) may include a plurality of co-extensive electrical protolayers ( 22, 23, 24 ) forming an electrical protolayer stack ( 20 ), at least selected or each electrical protolayer independently comprising at least 25 wt % sacrificial material and a thermally stable material and having a uniform thickness of less than 25 micrometers. The transfer films may include a plurality of co-extensive electrical protolayers forming an electrical protolayer stack, at least selected or each protolayer independently exhibiting a complex viscosity of between 10 3  and 10 4  Poise at a shear rate of 100/s when heated to a temperature between its Tg and T dec .

BACKGROUND

Many common electrical devices can be fabricated in a continuous manneron a flexible substrate. Continuous film-based methods have beendemonstrated for complete or partial fabrication of capacitors,resistors, thin film batteries, organic photovoltaics (OPVs), organiclight emitting diodes (OLEDs), and other components. However, there arefewer continuous techniques available for producing fully integratedmultilayer electrical films, especially those with a large number oflayers and electrodes, for example over 100 layers. Also, many thin filmelectrical devices are produced through multiple vapor deposition andpatterning steps. Accordingly, a need exists for complex electricaldevices and methods to fabricate them.

SUMMARY

The present disclosure relates to multilayer lamination transfer films,methods of forming these lamination transfer films and methods of usingthese lamination transfer films. These lamination transfer films utilizeelectrical protolayers that can be electrically coupled after a hightemperature step that removes sacrificial material and densifiesthermally stable material.

In one aspect, a transfer film includes a plurality of co-extensiveelectrical protolayers forming an electrical protolayer stack. At leastselected or each electrical protolayer independently comprises at least25 wt % sacrificial material and a thermally stable material and auniform thickness of less than 25 micrometers.

In another aspect, a transfer film includes a plurality of co-extensiveelectrical protolayers forming an electrical protolayer stack. At leastselected or each protolayer independently exhibits a complex viscosityof between 10³ and 10⁴ Poise at a shear rate of 100/s when heated to atemperature between its T_(g) and T_(dec).

In another aspect, a transfer film includes a plurality ofinterdigitated electrical protolayers forming an electrical protolayerstack. At least selected or each electrical protolayer independentlycomprises at least 25 wt % sacrificial material and a thermally stablematerial and a uniform thickness of less than 25 micrometers.

In a further aspect, a transfer film includes a plurality ofinterdigitated electrical protolayers forming an electrical protolayerstack. At least selected or each protolayer independently exhibits acomplex viscosity of between 10³ and 10⁴ Poise at a shear rate of 100/swhen heated to a temperature between its T_(g) and T_(dec).

In another aspect, a method includes laminating a transfer film,described herein, to a receptor substrate and baking out sacrificialmaterial to form an electrical stack.

In a further aspect, a method includes depositing a plurality ofinterdigitated electrical protolayers to form an electrical protolayerstack. Each protolayer independently has sacrificial material and athermally stable material and a uniform thickness of less than 25micrometers.

In still a further aspect, a method includes co-extruding a plurality ofinterdigitated electrical protolayers to form an electrical protolayerstack. Each protolayer independently includes a sacrificial material anda thermally stable material.

In still a further aspect, a method includes co-extruding a plurality ofelectrical protolayers to form an electrical protolayer stack. Eachprotolayer independently includes a sacrificial material and a thermallystable material.

These and various other features and advantages will be apparent from areading of the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure may be more completely understood in consideration of thefollowing detailed description of various embodiments of the disclosurein connection with the accompanying drawings, in which:

FIG. 1 is a schematic process flow diagram of an illustrative method offorming the transfer film and the electrical stack;

FIG. 2 is a schematic diagram of a three layer electrical stack with anegative and positive electrode formed by lamination transfer and bakingout;

FIG. 3 is a cross-sectional schematic diagram of a multilayerinterdigitated electrode film with buried electrodes and vertical busbars; and

FIG. 4 is a cross-sectional schematic diagram of a multilaneinterdigitated electrode film with horizontal bus bars.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings that form a part hereof, and in which are shown byway of illustration several specific embodiments. It is to be understoodthat other embodiments are contemplated and may be made withoutdeparting from the scope or spirit of the present disclosure. Thefollowing detailed description, therefore, is not to be taken in alimiting sense.

All scientific and technical terms used herein have meanings commonlyused in the art unless otherwise specified. The definitions providedherein are to facilitate understanding of certain terms used frequentlyherein and are not meant to limit the scope of the present disclosure.

Unless otherwise indicated, all numbers expressing feature sizes,amounts, and physical properties used in the specification and claimsare to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numericalparameters set forth in the foregoing specification and attached claimsare approximations that can vary depending upon the properties sought tobe obtained by those skilled in the art utilizing the teachingsdisclosed herein.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5) and any range within that range.

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” encompass embodiments having pluralreferents, unless the content clearly dictates otherwise.

As used in this specification and the appended claims, the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

As used herein, “have”, “having”, “include”, “including”, “comprise”,“comprising” or the like are used in their open ended sense, andgenerally mean “including, but not limited to”. It will be understoodthat “consisting essentially of”, “consisting of”, and the like aresubsumed in “comprising,” and the like.

In this disclosure:

“bake-out” refers to the process of substantially removing sacrificialmaterial present in a layer by pyrolysis, combustion, sublimation, orvaporization;“bake-out temperature” refers to the maximum temperature reached duringthe process of substantially removing sacrificial materials in a layerby pyrolysis, combustion, sublimation, or vaporization;“combust” or “combustion” refers to a process of heating a layer thatcomprises organic materials in an oxidizing atmosphere so that organicmaterials undergo a chemical reaction with the oxidant;“pyrolyze” or “pyrolysis” refers to a process of heating sacrificialmaterials in an inert atmosphere so that they decompose;“electrical protolayer” refers to a layer in the transfer film that is aprecursor layer to the electrical layer in the final baked outelectrical stack where the electrical layer functions as a conductor,insulator, functional electrode, electrolyte, oxidant, or reductant;“electrical stack” refers to two or more layers that in combinationproduce electrical effects. These effects could include phenomenaoccurring across the interfaces within the electrical stack such as ionconduction, electron conduction, charge separation, etc. The electricalstack can also exhibit composite performance including capacitance,energy storage, energy harvesting, etc. Other composite performanceattributes may include electrochromism, spatial light modulation, andother electro-optic phenomena.“thermally stable” refers to materials that remain substantially intactduring the removal of sacrificial materials, or chemical precursors tomaterials that remain substantially intact during the removal ofsacrificial materials.“densify” or “densification” refers to the process by which the weightand/or volume fraction of the thermally stable material is increasedduring the bake-out process. For example, in a densified layer the localconcentration (weight or volume %) of nanoparticles is increasedrelative to that in the protolayer. However, the average volume of theindividual nanoparticles may not change as a result of the densificationprocess.

The present disclosure relates to multilayer lamination transfer films,methods of forming these lamination transfer films, and methods of usingthese lamination transfer films. These multilayer lamination transferfilms utilize electrical protolayers that can be electrically coupledafter a high temperature step that removes sacrificial material anddensifies thermally stable material. Potentially, the process can beused to produce large area, filmless, durable inorganic electricaldevices such as electrochromic windows, photovoltaic devices,capacitors, supercapacitors, batteries, resistors, actuators, and energyharvesters, for example. Transfer films described herein include aplurality of co-extensive or interdigitated electrical protolayersforming an electrical protolayer stack. Each electrical protolayerindependently includes a sacrificial material and a thermally stablematerial and may have a thickness of less than 25 micrometers. In manyembodiments, at least selected or each electrical protolayerindependently has at least 25 wt % sacrificial material and a thermallystable material and a uniform thickness of less than 25 micrometers. Inmany embodiments, at least selected or each protolayer independentlyexhibits a complex viscosity of between 10³ and 10⁴ Poise at a shearrate of 100/s when heated to a temperature between its T_(g) andT_(dec). These electrical transfer films can be laminated onto athermally stable receptor substrate and baked out to form electricalstacks for use in devices such as, electrochromic windows, photovoltaicdevices, capacitors, supercapacitors, batteries, actuators, and energyharvesters that are all based on multilayer constructions with discretelayers that function as conductors, insulators, functional electrodes,electrolytes, oxidants, or reductants. Thus the electrical protolayersare precursors to inorganic electrical layers that function asconductors, insulators, oxidants, reductants, electrolytes, etc. Theelectrical protolayers can be formulated, coated, layered in a stack,and baked in such a way that the thermally stable components of theelectrical protolayers within the stack densify, stratify, andphysically bind together during the bake step. The use of electricalprotolayers allows for processing of inorganic materials at a low volumeloading (e.g. sub-percolation concentrations for conductive materials),enabling techniques such as thermoplastic extrusion of multilayers. Anynumber of electrical protolayers can be utilized such as 3 or more, 5 ormore, 10 or more, 25 or more, 50 or more, 100 or more, or 500 or more.While the present disclosure is not so limited, an appreciation ofvarious aspects of the disclosure will be gained through the discussionprovided below.

FIG. 1 is a schematic process flow diagram 50 of an illustrative methodof forming the transfer film 100 and the electrical stack 25. In someembodiments, the functional electrical device is completed by additionof a top electrode in a subsequent processing step. Any of theconventional means of electrode application may be used, including, forexample, vacuum deposition of conducting inorganic thin films,application of conductive inks, and application of conductive adhesivesor tapes.

The transfer film 100 includes a plurality of substantially parallellayers (or electrical protolayers) 22, 23 and 24 forming a protolayerstack 20. These substantially parallel layers (or electricalprotolayers) can be co-extensive as illustrated in FIG. 1 orinterdigitated as illustrated in FIG. 3 and FIG. 4. The substantiallyparallel layers can include offset electrical protolayers in theelectrical protolayer stack. Electrical protolayer stacks with offsetelectrical protolayers may have a small fraction of one or more of theelectrical protolayers extending from the electrical protolayer stack toallow for electrical connection in the baked-out electrical stack. Thefraction of the layer in the offset may be 25% of the layer width, or10% of the layer width, or 5% of the layer width, or 1% of the layerwidth, While FIG. 1 and FIG. 2 illustrate three electrical protolayers22, 23 and 24 forming a protolayer stack 20, it is understood that theprotolayer stack 20 can include any useful number of electricalprotolayers such as at least 3, at least 5, at least 10, at least 25, atleast 50, at least 100, or at least 500 electrical protolayers.

FIG. 2 is a schematic diagram of the electrical protolayer stack 20densification during the bake-out step. Each layer 22, 23 and 24independently includes a sacrificial material 26 and a thermally stablematerial 21 and is illustrated as generally uniform co-extensive but canbe interdigitated as illustrated in FIG. 3 and FIG. 4.

In many embodiments the protolayers 22, 23, and 24 each have a uniformthickness of less than 30 micrometers or less than 25 micrometers orless than 20 micrometers or less than 15 micrometers or are in a rangefrom 1 to 25 micrometers. In other embodiments the protolayers 22, 23,and 24 each have a uniform thickness of less than 1 micrometer or lessthan 750 nanometers or less than 500 nanometers or less than 250nanometers or are in a range from about 100 to about 1000 nanometers.

The formulation of each protolayer 22, 23, and 24 is tailored to providedifferent electrical properties in the final baked out electrical stack.

While the protolayer stack 20 is illustrated having three layers ofdiffering layer formulations 22, 23, and 24 (or A, B, and C), it isunderstood that protolayer stack 20 can have four different layerformulations A, B, C, and D or alternating layers such as A, B, A, B,etc. Other layer configurations are possible, including A, A, B, C; A,B, C, A; and layer configurations with repeating subsets of layer groups(e.g. [AB]_(x)[CD]_(y), A[BC]_(x)D, etc. where x and y are integersbetween 1 and 250.

The protolayer stack 20 can be deposited or formed on a polymericsupport layer or carrier layer 11 having a releasable surface 13. Thepolymeric support layer or carrier layer 11 can be implemented with athermally stable flexible film providing mechanical support for theprotolayer stack 20. The polymeric support layer 11 has a releasablesurface 13, meaning the polymeric support layer 11 allows for release ofprotolayer stack 20 applied to the releasable surface 13. The polymericsupport layer or carrier layer 11 can be thermally stable above 70° C.,or alternatively above 120° C. One example of a carrier film ispolyethylene terephthalate (PET).

Various polymeric film substrates comprised of various thermosetting orthermoplastic polymers are suitable for use as the polymeric supportlayer or carrier layer 11. The polymeric support layer or carrier layer11 may be a single layer or multi-layer film. Illustrative examples ofpolymers that may be employed as the carrier layer film include (1)fluorinated polymers such as poly(chlorotrifluoroethylene),poly(tetrafluoroethylene-co-hexafluoropropylene),poly(tetrafluoroethylene-co-perfluoro(alkyl)vinylether), poly(vinylidenefluoride-co-hexafluoropropylene); (2) ionomeric ethylene copolymerspoly(ethylene-co-methacrylic acid) with sodium or zinc ions such asSURLYN-8920 Brand and SURLYN-9910 Brand available from E. I. duPont deNemours, Wilmington, Del.; (3) low density polyolefins such as lowdensity polyethylene; linear low density polyethylene; and very lowdensity polyethylene; plasticized vinyl halide polymers such asplasticized poly(vinylchloride); (4) polyethylene copolymers includingacid functional polymers such as poly(ethylene-co-acrylic acid) “EAA”,poly(ethylene-co-methacrylic acid) “EMA”, poly(ethylene-co-maleic acid),and poly(ethylene-co-fumaric acid); acrylic functional polymers such aspoly(ethylene-co-alkylacrylates) where the alkyl group is methyl, ethyl,propyl, butyl, and the like, or CH₃(CH₂)_(n)— where n is 0 to 12, andpoly(ethylene-co-vinylacetate) “EVA”; and (5) (e.g.) aliphaticpolyurethanes. The polymeric support layer or carrier layer 11 can be anolefinic polymeric material, typically comprising at least 50 wt % of analkylene having 2 to 8 carbon atoms with ethylene and propylene beingmost commonly employed. Other polymeric support layers or carrier layers11 include for example poly(ethylene naphthalate), polycarbonate,poly(meth)acrylate (e.g., polymethyl methacrylate or “PMMA”),polyolefins (e.g., polypropylene or “PP”), polyesters (e.g.,polyethylene terephthalate or “PET”), polyamides, polyimides, phenolicresins, cellulose diacetate, cellulose triacetate (TAC), polystyrene,styrene-acrylonitrile copolymers, cyclic olefin copolymers, epoxies, andthe like. In some embodiments, the polymeric support layer or carrierlayer 11 can include paper, release-coated paper, non-wovens, wovens(fabric), metal films, and metal foils.

In some embodiments, the carrier layer 11 can include sacrificialmaterials that can remain on the protolayer stack 20 during the bake outprocess. For example, the carrier layer 11 can include a PMMA releaselayer on a PET layer where the release layer remains on the protolayerstack 20 following release from the PET layer. Sacrificial materials(such as the PMMA release layer), can be pyrolyzed by subjecting them tothermal conditions that can vaporize or decompose to volatile byproductssubstantially all of the organic material present in the sacrificiallayers. In these cases the layer can be called a sacrificial releaselayer. These sacrificial layers can also be subjected to combustion toburn out all of the organic material present in the sacrificial layer.Typically, a clear, high-purity polymer, such as poly(methylmethacrylate), or poly(ethyl acrylate-co-methyl methacrylate), can beused as the sacrificial material. Useful sacrificial materials leavevery low organic residue (ash) after pyrolysis or combustion at the bakeout temperature.

The protolayer stack 20 can be formed and applied to or disposed on(arrow 2) the support layer or carrier layer 11 by any useful method. Inmany embodiments, the protolayer stack 20 is formed by sequentiallyforming each layer 22, 23, 24 on each other. In other embodiments, theprotolayer stack 20 is formed by simultaneously extruding or formingeach layer 22, 23, 24. A sacrificial adhesive layer 29 can be applied toor disposed on (arrow 4) the protolayer stack 20 to assist in adheringthe protolayer stack 20 to the receptor substrate 40 during thelamination process (arrow 5). Alternatively, the sacrificial adhesivecan be applied to the receptor substrate, and the transfer filmsubsequently laminated in a “dry” transfer process. Independent of theprocess used to prepare it, this laminated transfer film/receptorsubstrate article 110 can then be baked out (arrow 8) to remove thesacrificial material 26 in the protolayers 22, 23, 24. The resultingbaked out article is an electrical stack 25. Sacrificial adhesive 29 andany release material 13 can be baked out also leaving the electricalstack 25 fixed to the receptor substrate 40.

The plurality of protolayers 22, 23 and 24 forming a protolayer stack 20can be deposited by any coating method or extrusion method, for example.To accomplish these coating or extrusion methods, each layer or selectedlayers in the protolayer stack can exhibit a complex viscosity ofbetween 10³ and 10⁴ Poise at a shear rate of 100/s when heated to atemperature between its T_(g) and T_(dec).

Examples of receptor substrates 40 include glass such as display motherglass (e.g., backplane mother glass), display cover glass, lightingmother glass, architectural glass, roll glass, and flexible glass. Anexample of flexible roll glass is commercially available under the tradedesignation WILLOW glass from Corning Incorporated. Other examples ofreceptor substrates include metals such as metal parts, sheets andfoils. Yet other examples of receptor substrates include sapphire,silicon, silica, and silicon carbide. In many embodiments the receptorsubstrates 40 is glass, quartz or sapphire. The receptor substrate cancomprise a collector electrode (bottom electrode), a transparentconductive oxide coating, a metal foil layer or coating, or a conductivethin film coating such as a thin metal film, a metal nanowire coating, aconductive polymer coating, a carbon nanotube coating, a graphenecoating, or a carbon black coating. Other exemplary receptors includesemiconductor materials on a support wafer as well as crystallinesupport wafers such as crystalline silicon, crystalline gallium nitride,crystalline indium phosphide, and crystalline gallium arsenide. Thereceptor substrates 40 can be flat, or curved.

Display backplane mother glass receptor substrates can optionallyinclude a buffer layer on a side of the receptor substrate to which alamination transfer film is applied. Examples of buffer layers aredescribed in U.S. Pat. No. 6,396,079, which is incorporated herein byreference as if fully set forth. One type of buffer layer is a thinlayer of SiO₂, as described in K. Kondoh et al., J. of Non-CrystallineSolids 178 (1994) 189-98, and T-K. Kim et al., Mat. Res. Soc. Symp.Proc. Vol. 448 (1997) 419-23, both of which are incorporated herein byreference as if fully set forth.

A particular advantage of the transfer films and methods describedherein is the ability to impart an electrical stack to a substrate witha large surface area, such as display mother glass, photovoltaic glass,or architectural glass. The transfer films 100 described herein havelarge enough dimensions to be used to impart an electrical stack over,at least, entire large digital display substrates (e.g., a 55 inchdiagonal AMOLED HDTV, with dimensions of 52 inches wide by 31.4 inchestall) or photovoltaic module, with dimensions of 1 meter by 1.6 meter,for example.

The sacrificial material in each layer of the protolayer stack 20 can becleanly baked out leaving a densified layer of thermally stable materialdefining each layer of the electrical stack 25. In some embodiments, thedensified layers of thermally stable material can completely orpartially fuse into a glass-like material. FIG. 2A to 2C are schematicdiagrams of the electrical protolayer stack 20 densification during thebake out step. In some embodiments, the densified layers are not fullydense and have some porosity. Densified layers may have less than 70%porosity, or less than 60% porosity, or less than 50% porosity, or lessthan 40% porosity, or less than 30% porosity, or less than 20% porosity,or less than 10% porosity, or less than 5% porosity. Densified layersmay have greater than 70% porosity, or greater than 60% porosity, orgreater than 50% porosity, or greater than 40% porosity, or greater than30% porosity, or greater than 20% porosity, or greater than 10%porosity, or greater than 5% porosity. In some embodiments, thedensified layers have from about 5% porosity to about 70%, from about 5%porosity to about 60%, from about 5% porosity to about 50%, from about5% porosity to about 40%, from about 5% porosity to about 30%, fromabout 5% porosity to about 20%.

A liquid or fluid can then be infused into the porous layer if desired.Liquids may be electrically active liquids and include electrolytes,ionic liquids, liquid crystals, monomer dispersed liquid crystals foruse in polymer dispersed liquid crystals, electroactive dyes in solvent,pigment dispersion, or ferrofluids, etc.

FIG. 2 illustrates a protolayer stack 20 formed of three co-extensiveelectrical protolayers 22, 23, and 24 stacked on each other. A magnifiedview of layer 22 is illustrated as 2A and shows the thermally stablematerial 21 dispersed in the sacrificial material 26. It is understoodthat the layers 23 and 24 also include thermally stable materials(optionally different than the thermally stable material 21) dispersedin the sacrificial material. In many embodiments the sacrificialmaterial is the same kind or same material in each layer forming theelectrical protolayer stack 20. In other embodiments the electricalprotolayers have different kinds or types of sacrificial materialforming each protolayer. The thermally stable material 21 can be presentin each protolayer in a range from 1 to 75% wt, or less than 75% wt, orless than 50% wt, or less than 25% wt, or less than 10% wt. In someembodiments, the thermally stable material may be present in eachprotolayer in a range from about 1 to about 75 weight percent, fromabout 1 to about 65 weight percent, from about 1 to about 50 weightpercent, from about 1 to about 25 weight percent or even from about 1 toabout 10 weight percent. In many embodiments the thermally stablematerial 21 is inorganic nanomaterial. In some embodiments, thethermally stable material may include from about 0 to about 75 weightpercent, from about 0 to about 65 weight percent, from about 0 to about50 weight percent, from about 10 to about 75 weight percent, from about10 to about 65 weight percent, or even from about 10 to about 50 weightpercent inorganic nanomaterial

FIG. 2B illustrates an electrical protolayer stack 20 where a portion ofthe sacrificial material 26 is removed via bake out for example. Amagnified view of layer 22 is illustrated as 2B and shows the thermallystable material 21 slightly densified in the sacrificial material 26.

FIG. 2C illustrates an electrical stack 25 where the sacrificialmaterial 26 is removed via bake out for example. A magnified view oflayer 22 is illustrated as 2C and shows the thermally stable material 21densified and forming the electrical stack 25.

The layers forming the electrical stack 25 are co-extensive orinterdigitated with each other and each layer has a uniform thickness ofless than 10 micrometers, or less than 5 micrometers, or less than 3micrometers or less than 2 micrometers or less than 1 micrometer or isin a range from 500 nanometers to 2 micrometers. In other embodimentsthe layers forming the electrical stack 25 are co-extensive orinterdigitated with each other and each layer has a uniform thickness ofless than 500 nanometers or less than 250 nanometers or less than 100nanometers or are in a range from 40 nanometers to 500 nanometers.

FIG. 3 is a cross-sectional schematic diagram of a multilayerinterdigitated electrode stack 10 with buried electrodes and verticalbus bars 18, 20. FIG. 4 is a cross-sectional schematic diagram of amultilane interdigitated electrode stack 34 with horizontal bus bars 42,44. These stacks 10, 34 have a first major surface and a second majorsurface opposite the first major surface, and in-plane directiongenerally along the first and second major surfaces. The stacks aredescribed with reference to the x, y, and z directions. The x directionis along the length of the stack (along a machine direction), the ydirection is along the width of the stack, and the z direction is alonga distance between the first and second major surfaces.

The multilayer interdigitated electrode stack 10 includes electrodelayers 12 interdigitated with electrode layers 14 between the majorsurfaces along the in-plane direction of the stack 10. Insulating layers16 separate the electrode layers 12, 14. A bus bar 18 electricallyconnects and is integrated with electrode layers 12 at one locationbetween the major surfaces of the stack 10 along the z-direction, forexample along a first edge of the stack. A bus bar 20 electricallyconnects and is integrated with electrode layers 14 at one locationbetween the major surfaces of the stack 10 along the z-direction, forexample along a second edge of the stack opposing the first edge.Optional skin layers 15 and 17 can be located on the major surfaces ofthe stack 10.

The multilane interdigitated electrode stack 34 includes electrodelayers 36 interdigitated with electrode layers 38 between the majorsurfaces along the z-direction. Insulating layers 40 separate theelectrode layers 36, 38 from each other. A bus bar 44 electricallyconnects and is integrated with electrode layers 36 on one major surfaceof the stack 34 along the in-plane direction, and a bus bar 42electrically connects and is integrated with electrode layers 38 on theopposing major surface of the stack 34 along the in-plane direction.

Protolayers are precursors to the inorganic layers of the finalelectrical article. The protolayers may include a thermally stablematerial and a sacrificial material. The protolayers may also includeorganometallic compounds, i.e. organometallic precursors that have boththermally stable moieties and sacrificial moieties. The protolayers mayinclude nanomaterials, organometallic compounds, and sacrificialmaterials. Before the thermal process (i.e., bake-out), the protolayersare processable (e.g. at least one of extrudable, coatable, and curable)and may not possess the requisite electrical properties of the finalelectrical article. After transfer to a thermally stable surface, theprotolayers are baked to form inorganic layers with desired physical,chemical, and electrical properties during a thermal bake-out step. Thetransformation may involve depolymerization of a sacrificial binder,decomposition of an organometallic polymer or coordination compound,densification of nanoparticles, chemical oligomerization or reaction oforganosilanes, etc.

Protolayers and/or layers of the final electrical stack can function asconductors, insulators, functional electrodes, electrolytes, oxidants,or reductants. The electrical protolayers can be formulated, coated,layered in a stack, and baked in such a way that the thermally stablecomponents of the electrical protolayers within the stack densify,stratify, and physically bind together during the bake-out step. The useof electrical protolayers allows for processing of inorganic materialsat a low volume loading (e.g. sub-percolation concentrations forconductive materials), enabling techniques such as thermoplasticextrusion of multilayers.

Protolayers and/or layers of the final electrical stack can beelectrically conducting or electrically insulating. In some embodiments,the electrical protolayer stack includes an electrode protolayer havingelectrically conductive material and a dielectric protolayer havingelectrically insulating material.

In some embodiments, the electrical protolayer stack includes a negativeelectrode protolayer having negative electrode material, a positiveelectrode protolayer having positive electrode material and anelectrolyte protolayer having electrolyte material. The electrolyteprotolayer is disposed between the negative electrode protolayer and thepositive electrode protolayer.

In some embodiments, the electrical protolayer stack includes aplurality of electrochromic protolayers having electrochromic materialsand an electrolyte protolayer having an electrolyte material.

In further embodiments, the protolayer stack includes a first pluralityof electrical protolayers interdigitated with a second plurality ofelectrical protolayers.

One illustrative example of a protolayer formulation comprises asacrificial thermoplastic or thermoset (e.g. a polyethylene oxide,alkylene polycarbonate, or photocured acrylic), an inorganicnanoparticle (e.g. BaTiO₃), and an organosilane (e.g. oligomeric methylsilsesquioxane). During bake out, the sacrificial binder is removed, theparticles are densified, and the organosilane remains as an inorganicbinder to provide mechanical integrity to the barium titanate layer.

Another illustrative example of a protolayer formulation comprisesinorganic nanoparticles and an organometallic polymer or coordinationcompound (e.g. a metallo polyethyleneimine or metal salt of apolycarboxylated polymer). The polymer undergoes decomposition and,depending upon the atmosphere during decomposition, can be transformedinto a metal oxide, nitride, or carbide. In this case, theorganometallic polymer has both sacrificial (carbon backbone) andinorganic (complexed metals) components. This type of system has beenstudied for “polymer assisted deposition” (G. F. Zou et al, Chem. Soc.Rev. 2013, 42, 439-449). The systems are particularly useful for in situsynthesis of complex mixed oxides such as tin or zinc doped indiumoxides and other transparent conductive oxides.

Yet another illustrative example of a protolayer formulation comprises asacrificial polymer, inorganic nanoparticles, and a polymer known toproduce graphitic carbon upon thermal decomposition (e.g. a resorcinolformaldehyde oligomer). If the inorganic nanoparticles are carbonnanotubes, the sacrificial polymer is removed during decomposition andthe resorcinol formaldehyde oligomer and nanotubes are transformed to aconductive carbon layer composite. Other combinations of materials arepossible. For example, it would be desirable to increase conductivity inan inorganic layer by including metal nanowires or nanoparticles in aformulation with a graphitic carbon precursor and a sacrificialthermoplastic. After heating to remove the sacrificial polymer theresulting layer would be a composite of graphitic carbon and conductivenanoparticles or wires.

Protolayer formulations with thermoplastic characteristics may beextruded, molded, or (if soluble) solvent cast. Protolayer formulationswith thermoset characteristics may be applied by solvent castingfollowed by solvent removal and thermal or photochemical curing steps.Each of these methods is compatible with roll to roll processing.Multilayers may be obtained by appropriate techniques includingmultilayer extrusion (e.g., U.S. Pat. No. 6,827,886) or multilaneextrusion (e.g., U.S. Ser. No. 13/775,415), multilayer coating, or slidecoating. Interdigitation of the protolayers is possible (e.g., U.S. Ser.No. 13/775,415). The type of interdigitation can be based upon, forexample, a desired performance or application of the electricalprotolayer stack. The amount of overlap between the interdigitatedelectrical protolayers can also be varied by increasing or decreasingthe amount of overlap, or by purposefully smoothing or sharpeningindividual elements of the interdigitated protolayers to affect theperformance of the electrical stack, for example.

The electrical stacks described herein can be used to produce largearea, filmless, durable inorganic electrical devices such aselectrochromic windows or devices, photovoltaic devices, capacitors,supercapacitors, batteries, resistors, actuators, and energy harvesters,for example.

Thermally Stable Material

A thermally stable material is utilized to form a layer, e.g. anelectrical protolayer, in the electrical stack. The thermally stablematerial can be densified or chemically transformed to form theinorganic electrical stack. The thermally stable material includesthermally stable molecular species, for example. It is understood thatthe thermally stable material may include precursor materials thateither are or transform into materials that remain substantially intactduring the removal of sacrificial materials, such as during “bake-out”or pyrolysis. Thermally stable materials may include inorganicnanoparticles, electrochromic materials, photochromic materials,conducting materials, dielectric materials, and battery materials. Insome embodiments, the thermally stable material may include inorganicmaterials that may be formed, for example, from precursors, particularlyorganometallic precursors, i.e. organometallic reagents. Theorganometallic precursors may have both thermally stable moieties andsacrificial moieties. Upon thermal treatment, e.g. bakeout, ofprotolayers that include organometallic precursors, the thermally stablemoieties may be transformed into a thermally stable material, e.g. ametal oxide, and the sacrificial moieties may be removed from theprotolayer.

The thermally stable material may include organometallic precursors. Theorganometallic precursors may be at least one of small moleculeorganometallic precursors, oligomeric organometallic precursors, andpolymeric organometallic precursors. The organometallic precursors mayreact, for instance upon heating and/or condensation, to form metaloxides, for example. The organometallic precursors that chemicallytransform, e.g. reacts, into a metal oxide may do so concurrently withremoval of sacrificial material. Combinations of at least two or more ofthe small molecule precursors, oligomer precursors and polymericprecursors may be used. The organometallic precursors; i.e. smallmolecule organometallic precursors, oligomeric organometallic precursorsand polymeric organometallic precursors; may include, but are notlimited to, aluminum oxide; barium titanium oxide; indium oxide whichmay be doped with tin, gallium, zinc, and the like; tin oxide, which mayalso be doped with, for instance, antimony or fluorine; zirconium oxide;titanium oxide; silicon oxide; zinc oxide, optionally doped with, forinstance, fluorine, aluminum, or yttrium; iron oxide; calcium oxide;magnesium oxide; manganese oxide; chromium oxide; copper oxide; vanadiumoxide; nickel oxide; barium oxide; strontium oxide; cobalt oxide;niobium oxide; molybdenum oxide; and tungsten oxide organometallicprecursors. Combinations may be used to form mixed metal oxidematerials. These precursors can be an excellent route to metal oxides,as their pyrolysis in oxygen or air induces decomposition of theprecursor, oxidation of the organic ligand portion to volatilefragments, and formation of metal oxide residue. The precursors may alsoexhibit excellent solubility in organic media, and thus can beformulated with organic polymers and UV-curable resins to fabricate theprotolayers of the present disclosure. Nonlimiting examples of metaloxides accessible by this route include oxides of silicon, aluminum,zinc, tin, indium, zirconium, titanium, vanadium, nickel, barium,strontium, niobium, molybdenum, and tungsten. Fluorine-doped metaloxides such as F-doped zinc oxide and F-doped tin oxide can also beprepared by decomposition of organometallic compounds bearingfluorine-containing ligands, such as trifluoroacetate andtrifluoroacetonate. Other inorganic species such as metals and metalsulfides can also be prepared in this manner using appropriately chosenorganometallic precursors and careful control of the atmosphere duringthe bakeout to drive off the sacrificial binder. For example, productionof metal coatings may be achieved using a reducing environment in placeof air, and metal sulfides may be prepared by pyrolysis in a hydrogensulfide atmosphere.

Small-molecule organometallic precursors include, but are not limitedto, metal carboxylate salts such as metal acetates and metal2-ethylhexanoates; metal ketonates such as metal acetylacetonates, metal(2,2,6,6-tetramethylheptanedionate)s, and metal(methyltrimethylacetylacetate)s; metal dialkylimides such as metaldimethylimides; and metal alkoxides such as metal ethoxides and metalisopropoxides. Other ligands such as thiourea, pyridine andalkyl-substituted pyridines, and halides can also be used, and the aboveligands can be used alone or in combination, such as in mixedcarboxylate-pyridine complexes or compounds containing acetylacetonateas well as chloride ligands. The above ligands may be suitable foroligomeric and/or polymeric organometallic precursors. Combinations ofdifferent small molecule precursors may be used. Small moleculeorganometallic precursors may have a molecular weight range, forinstance, from about 200 g/mol to less than about 600 g/mol.

When using small molecule organometallic precursors, a competition mayarise between decomposition and volatilization of the organometallicprecursor during the bakeout step. Volatilization is undesirable becauseit may lower the yield of inorganic material of the thermally stablematerial. Loss of small molecule organometallic precursor byvolatilization may be reduced or eliminated through the use ofoligomeric and/or polymeric organometallic precursors.

Oligomeric and polymeric organometallic precursors may be pre-formed andused as the source of the inorganic material of the thermally stablematerial in the protolayers, as exemplified by commercial products suchas aluminum oxide, polymeric precursor, 10% w/v solution in toluene(catalog number 42767); barium titanate oxide, polymeric precursor,oxide approx. 35 wt. % (catalog number 39755); indium oxide, tin doped,polymeric precursor, oxide approx. 20 wt. % (catalog number 42229); andzirconium oxide, polymeric precursor (catalog number 42766), allavailable from Alfa Aesar, Ward Hill, Mass., and a barium strontiumtitanate polymeric precursor available under the trade designationSERAMIC BST from Gelest, Inc., Morrisville, Pa. These products aresolutions of organic-functional polymeric or oligomeric metal oxideprecursors in organic solvents such as alcohols or toluene. They can becoated on inorganic substrates, for example glass, and may be pyrolyzedin air to produce metal oxides in high yields. Oligomeric organometallicprecursors may have a molecular weight range from about 600 g/mol toless than about 2000 g/mol. Combinations of different oligomericorganometallic precursors may be used. Polymeric organometallicprecursors may have a molecular weight range from about 2000 g/mol toabout 1,000,000 or even greater. In some embodiments, polymericorganometallic precursors may have a molecular weight range from about5000 g/mol to about 1,000,000 or even greater.

Polymeric inorganic precursors can also be generated by reaction ofmonomeric organometallics such as metal acetylacetonates or metalcarboxylates with functional group-bearing polymers such as(meth)acrylic acid copolymers or copoly(meth)acrylic acid precursors.Species such as metal acetylacetonates may be used to crosslink acrylicacid-containing copolymers; this occurs through ligand exchangereactions in which the carboxyl groups on the polymer displace theacetylacetonate ligands. Occurrence of this reaction can be delayed,enabling preparation of stable coating formulations, by masking orprotecting the carboxyls in another chemical form exhibiting greatlyreduced reactivity with the organometallic reagent, and thendeprotecting in a later step. This can be accomplished in a number ofways. One embodiment involves first neutralizing a solution of thecarboxyl-functional polymer with a volatile amine such as triethylamineor dimethylethanolamine before addition of the metal acetylacetonate.The resulting ammonium carboxylate reacts much less rapidly with themetal acetylacetonate or metal carboxylate. Once the organometallicreagent is added, the coating formulation is much more stable than inthe absence of the amine; when the mixture is coated and dried, thevolatile amine is liberated resulting in regeneration of the carboxylgroups. The carboxyl groups then undergo rapid ligand exchange with theorganometallic to form the polymeric metal carboxylate in situ. The sameend result can also be achieved using highly-substituted alkyl(meth)acrylates such as t-butyl (meth)acrylate as a masked or latentform of (meth)acrylic acid. (Co)polymers of t-butyl (meth)acrylateliberate isobutene on heating, leaving a carboxyl-functional polymerbehind. Thus, the t-butyl ester groups perform the equivalent functionas the amine-neutralized carboxyls described above, resulting inpolymeric metal carboxylates formed in situ. Baking burns off theorganic polymeric portion of the coating, generating the metal oxide.These materials can function as the thermally stable material of theprotolayers of the present disclosure.

Another approach to polymeric inorganic precursors involves in-situcopolymerization of acrylic-functional organometallic species withacrylic monomers or resins. Some acrylic-functional inorganics arecommercially available, such as zinc dimethacrylate, available under thetrade designation SR-708, from Sartomer Americas, Exton, Pa. However,these species can have limited solubility in organic solvents andlimited compatibility with other acrylic resins, so other analogues withhigher organic content and hence better organic compatability can beutilized such as those materials described in U.S. Pat. No. 6,399,672,which is incorporated herein by reference in its entirety. Stablecoating formulations containing these metal-functional acrylates andother acrylic monomers and resins can be prepared, coated, dried, andcured to generate polymeric inorganic precursors for use as thethermally stable material of the protolayers of the present disclosure.Such precursors can also be generated in-situ, such as through treatmentof organometallic compounds such as metal acetoacetonates, metalalkoxides, or metal carboxylates with functional group-bearing acrylicmonomers such as acetylacetoxyethyl (meth)acrylate, acrylic acid, orbeta-carboxyethyl acrylate. Such acrylate monomers are capable ofreacting into the ligand sphere of the organometallic, generatingacrylic-functional organometallic species that can be coated and curedto generate the thermally stable material of the protolayers of thepresent invention. Examples of metal alkoxide-derived acrylic-functionalprecursor resins are described in S. S. Dinachali et al, Adv. Funct.Mater. 2013, 23, 2201-2211.

In many embodiments the thermally stable material includes inorganicnanoparticles or nanomaterial. These inorganic nanoparticles ornanomaterial can be of various sizes and shapes. The inorganicnanoparticles or nanomaterial can have an average particle diameter lessthan about 1000 nm, less than about 750 nm, less than about 500 nm, lessthan about 250 nm, less than about 100 nm, less than about 50 nm, orless than about 35 nm. The inorganic nanoparticles or nanomaterial canhave an average particle diameter from about 3 nm to about 1000 nm, fromabout 3 nm to about 750 nm, from about 3 nm to about 500 nm, from about3 nm to about 250 nm, from about 3 nm to about 50 nm, or from about 3 nmto about 35 nm, or from about 5 nm to about 25 nm. If the nanoparticlesare aggregated, the maximum cross sectional dimension of the aggregatedparticle can be within any of these ranges, and can also be greater thanabout 100 nm. Various shapes of the inorganic nanoparticles ornanomaterial may be used, such as sphere, rod, sheet, tube, wire, cube,cone, tetrahedron, and the like. In some embodiments, the thermallystable material may include from about 0 to about 75 weight percent,from about 0 to about 65 weight percent, from about 0 to about 50 weightpercent, from about 10 to about 75 weight percent, from about 10 toabout 65 weight percent, or even from about 10 to about 50 weightpercent inorganic nanoparticles.

The nanomaterial selected can impart various optical properties (i.e.refractive index, birefringence), electrical properties (e.g.conductivity), mechanical properties (e.g. toughness, pencil hardness,scratch resistance) or a combination of these properties. Examples ofsuitable inorganic nanoparticles or nanomaterial include metalnanoparticles or their respective oxides, including the elementszirconium (Zr), titanium (Ti), hafnium (Hf), aluminum (Al), iron (Fe),vanadium (V), antimony (Sb), tin (Sn), gold (Au), copper (Cu), gallium(Ga), indium (In), chromium (Cr), manganese (Mn), cobalt (Co), nickel(Ni), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), technetium(Te), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium(Cd), lanthanum (La), tantalum (Ta), tungsten (W), rhenium (Rh), osmium(Os), iridium (Ir), platinum (Pt), cerium (Ce), strontium (Sr) and anycombinations thereof (indium tin oxide, for example).

Further examples of suitable inorganic nanoparticles or nanomaterialinclude fluorides such as, magnesium fluoride, calcium fluoride, leadfluoride, aluminum fluoride and barium fluoride. Further examples ofsuitable inorganic nanoparticles include nitrides such as siliconnitride and boron nitride. Further examples of suitable inorganicnanoparticles or nanomaterial include mixed metal titanates such asstrontium titanate, barium titanate and barium strontium titanate.Further examples of suitable inorganic nanoparticles include mixed metaloxides (for example, aluminosilicates), mixed metal fluorides, and mixednitrides.

Other examples of suitable inorganic nanoparticles or nanomaterialinclude elements and alloys known as semiconductors and their respectiveoxides such as silicon (Si), germanium (Ge), silicon carbide (SiC),silicon germanide (SiGe), carbon (e.g. carbon nanotubes or graphenenanoplatelets), aluminium nitride (AlN), aluminum phosphide (AlP), boroncarbide (B₄C), gallium antimonide (GaSb), indium phosphide (InP),gallium arsenide nitride (GaAsN), gallium arsenide phosphide (GaAsP),indium aluminum arsenide nitride (InAlAsN), zinc oxide (ZnO), zincselenide (ZnSe), zinc sulfide (ZnS), zinc telluride (ZnTe), mercury zincselenide (HgZnSe), lead sulfide (PbS), lead telluride (PbTe), tinsulfide (SnS), lead tin telluride (PbSnTe), thallium tin telluride(Tl₂SnTes), zinc phosphide (Zn₃P₂), zinc arsenide (Zn₃As₂), zincantimonide (Zn₃Sb₂), lead(II) iodide (PbI₂), and copper(I) oxide (Cu₂O).

Examples of suitable inorganic nanoparticles or nanomaterial includeelements known as rare earth elements and their oxides, such as theoxides of lanthanum (La₂O₃), cerium (CeO₂), praseodymium (Pr₆O₁₁),neodymium (Nd₂O₃), samarium (Sm₂O₃), europium (Eu₂O₃), gadolinium(Gd₂O₃), terbium (Tb₄O₇), dysprosium (Dy₂O₃), holmium (Ho₂O₃), erbium(Er₂O₃), thulium (Tm₂O₃), ytterbium (Yb₂O₃) and lutetium (Lu₂O₃).

Electrochromic materials include but are not limited to at least one of,for example: polyoxometallates (e.g. PW₁₂O₄₀ ³⁻, SiW₁₂O₄₀ ⁴⁻, W₁₀O₃₂ ³⁻,[Eu—(H₂O)P₅W₃₀O₁₁]¹²⁻); tungsten oxide (WO₃); iridium oxide (IrO₂,Ir(OH)₃); nickel oxide; hydrous nickel oxide; molybdenum oxide (MoO₃);tin oxide (SnO₂); vanadium oxide (V₂O₅) and lithiated vanadium oxidessuch as described in U.S. Pat. No. 6,177,130, incorporated herein byreference in its entirety; niobium oxide (Nb₂O₅); and titanium oxide(TiO₂), transition metal oxides of manganese, cobalt, rhodium, andruthenium, Prussian Blue (Fe(III)₄[Fe(II)(CN)₆]₃ orKFe(III)Fe(II)(CN)₆), and metal phthalocyanines (those with sufficientthermal stability). Other materials which can be utilized inelectrochromic constructions are described in U.S. Pat. Publ. No.2012/0200908; C. G. Granqvist, “Oxide electrochromics: An introductionto devices and materials”, Solar Energy Materials & Solar Cells, 2012,Vol. 99, pp. 1-13; and C. G. Granqvist, “Electrochromics for smartwindows: Oxide-based thin films and devices”, Thin Solid Films, 2014,Vol. 564, pp. 1-38, all incorporated herein by reference in theirentirety.

Dielectric material includes but is not limited to at least one of, forexample: titanium dioxide; strontium titanate; barium strontiumtitanate; barium titanate; lead zirconium titanate; calcium coppertitanate; silicon dioxide; hafnium silicate; zirconium silicate; hafniumdioxide; and zirconium dioxide.

Positive electrode materials, used in batteries for example, include butare not limited to at least one of, for example: LiMO₂ or LiMS₂, where Mcan be Ti, V, Cr, Mn, Fe, Co, Ni, Mo and mixtures thereof; LiM₂O₄, whereM can be Ti, V, Cr, Mn, Fe, Co, Ni, Mo and mixtures thereof; LiMPO₄,where M can be Ti, V, Cr, Mn, Fe, Co, Ni, and mixtures thereof; and asolid solution of Li₂MnO₃ with LiMO₂, where M can be Ti, V, Cr, Mn, Fe,Co, Ni, and mixtures thereof.

Negative electrode materials, used in batteries for example, include butare not limited to at least one of, for example, Li₄Ti₅O₁₂ (lithiumtitanium oxide); Natural or synthetic graphite; Si or Si/graphitecomposites; Si alloys including one or more of Li, Mg, Al, B, P, S, O,C, Ti, Ti, V, Cr, Mn, Fe, Co, Ni, Mo, Zn, Zr; and other alloys thatcontain at least one or more of Ge, Sn, Pb, B, Al, As and Sb.

Electrolyte materials are electrically insulating but allow ions such asLi ions to transport through them. In some embodiments, the electrolytematerials may be solid state electrolyte materials. Solid stateelectrolyte materials include, but are not limited to, at least one of,for example, LiSICONs such as LiPON, Li₁₄Zn(GeO₄)₄,Li_(0.36)Si_(0.6)P_(0.4)O₄, and glasses such as Li₂S—P₂S₅,Li₂S—SiS₂—Li₃PO₄, and glass-ceramics such as Li₇P₃S₁₁,Li_((1+x))Ge_((2-x)) Alx(PO₄)₃, and ceramics such as Li-beta-Al₂O₃,Li₃N, doped Li₃N, La_(0.5)Li_(0.5)TiO₃, and thiophosphates such asLi_(3.25)Ge_(0.25)P_(0.75)S₄, Li₁₀GeP₂Si₂.

In some embodiments, the thermally stable layer may include a porousinorganic dielectric layer. The pores of the porous inorganic dielectriclayer may be at least partially filled with an electrically activeliquid, e.g. a liquid electrolyte. The liquid electrolyte may be thoseknown in the art. In some embodiments, the liquid electrolyte is atleast one of a solvent and a salt. Exemplary liquid electrolytes aredescribed in U.S. Pat. Publ. No. 2012/0200908; C. G. Granqvist, “Oxideelectrochromics: An introduction to devices and materials”, Solar EnergyMaterials & Solar Cells, 2012, Vol. 99, pp. 1-13; and C. G. Granqvist,“Electrochromics for smart windows: Oxide-based thin films and devices”,Thin Solid Films, 2014, Vol. 564, pp. 1-38, all incorporated herein byreference in their entirety

Sacrificial Materials

The sacrificial material is a material capable of being baked out orotherwise removed while leaving the thermally stable material,substantially intact. The sacrificial material includes, for example,the sacrificial material within each protolayer and the optionalsacrificial releasable layer and the optional sacrificial adhesivelayer, depending upon a construction of the transfer film. Thesacrificial material may be a polymer, e.g. an organic polymer. Thesacrificial material may be the reaction product of a polymerizablecomposition, which forms a polymer, and/or may be a polymer, e.g. apreviously formed polymer. In many embodiments, the sacrificial materialis made from a polymerizable composition, i.e. the sacrificial materialmay be the reaction product of a polymerizable composition. Thepolymerizable composition may include monomer, oligomer and/or polymer.The sacrificial material may be a thermoplastic. A thermoplastic may beformed from a polymerizable composition that contains monomer, oligomerand/or polymer that chain extends to form a polymer that issubstantially free of cross-linking. The sacrificial material may be athermoset. A thermoset may be formed from a polymerizable compositionthat contains monomer, oligomer and/or polymer that crosslink to form apolymer that includes a cross-linked network. In the formation of athermoset, the monomer, oligomer and/or polymer of the polymerizablecomposition may also chain extend, increasing the molecular weight ofthe polymer segment between crosslinks. In many embodiments, thesacrificial material is present in each electrical protolayer in a rangefrom about 25 to about 95 wt %, from about 30 to about 95 wt %, fromabout 40 to about 95 wt % or even from about from about 50 to about 95wt %. In some embodiments the sacrificial material is present in eachelectrical protolayer may be at least 30 wt %, at least 40 wt %, or evenat least 50 wt %.

Useful polymerizable compositions comprise curable functional groupsknown in the art, such as epoxide groups, allyloxy groups,(meth)acrylate groups, vinyl, hydroxyl, carboxylic acid, amino,phenolic, aldehyde, cinnamate, alkene, alkyne, ethylenically unsaturatedgroups, vinyl ether groups, and any derivatives and any chemicallycompatible combinations thereof.

The polymerizable composition used to prepare the sacrificial materialmay contain monofunctional or multifunctional (e.g, di-, tri-, andtetra-) curable moieties, e.g. monomers and/or oligomers. Examples ofsuitable monofunctional polymerizable precursors useful in preparationof sacrificial polymeric materials include styrene, alpha-methylstyrene,substituted styrene, vinyl esters, vinyl ethers, octyl (meth)acrylate,nonylphenol ethoxylate (meth)acrylate, isobornyl (meth)acrylate,isononyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate,2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, beta-carboxyethyl(meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,cycloaliphatic epoxide, alpha-epoxide, 2-hydroxyethyl (meth)acrylate,isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-butyl (meth)acrylate,methyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic acid,N-vinylcaprolactam, stearyl (meth)acrylate, hydroxyl functionalcaprolactone ester (meth)acrylate, isooctyl (meth)acrylate,hydroxypropyl (meth)acrylate, hydroxyisopropyl (meth)acrylate,hydroxybutyl (meth)acrylate, hydroxyisobutyl (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, acetoacetoxyalkyl (meth)acrylatessuch as acetoacetoxyethyl methacrylate, and any combinations thereof.

Examples of suitable multifunctional polymerizable precursors includeethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate,triethylene glycol di(meth)acrylate, tetraethylene glycoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, glyceroltri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol Adi(meth)acrylate, poly(1,4-butanediol) di(meth)acrylate, anysubstituted, ethoxylated or propoxylated versions of the materialslisted above, or any combinations thereof.

The polymerization reactions may lead to the formation of athree-dimensional “crosslinked” macromolecular network and are alsoknown in the art as negative-tone photoresists, as reviewed by Shaw etal., “Negative photoresists for optical lithography,” IBM Journal ofResearch and Development (1997) 41, 81-94. The formation of the networkmay occur through either covalent, ionic, or hydrogen bonding, orthrough physical crosslinking mechanisms such as chain entanglement. Thereactions can also be initiated through one or more intermediatespecies, such as free-radical generating photoinitiators,photosensitizers, photoacid generators, photobase generators, or thermalacid generators. The type of curing agent used depends on thepolymerizable precursor used and on the wavelength of the radiation usedto cure the polymerizable precursor. Examples of suitable commerciallyavailable free-radical generating photoinitiators include benzophenones,benzoin ethers, and acylphosphine photoinitiators, such as those soldunder the trade designations “IRGACURE” and “DAROCUR” from CibaSpecialty Chemicals, Tarrytown, N.Y. Other exemplary photoinitiatorsinclude 2,2-dimethoxy-2-phenylacetophenone (DMPAP),2,2-dimethoxyacetophenone (DMAP), xanthone, and thioxanthone.Co-initiators and amine synergists may also be included to improvecuring rates of the polymerizable compositions. Suitable concentrationsof the curing agent in the crosslinking matrix range from about 1 wt %to about 10 wt %, with particularly suitable concentrations ranging fromabout 1 wt % to about 5 wt %, based on the entire weight of thepolymerizable precursor.

Other materials that may be used for the sacrificial material include,polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyethyleneimine(PEI), ethylcellulose, methylcellulose, polynorbornenes,poly(methylmethacrylate (PMMA), poly(vinylbutyral), poly(cyclohexenecarbonate), poly(cyclohexene propylene) carbonate, poly(ethylenecarbonate), poly(propylene carbonate) and other aliphaticpolycarbonates, and any copolymer or blends thereof, and other materialsdescribed in R. E. Mistler and E. R. Twiname, Tape Casting: Theory andPractice, American Ceramic Society, 2000, chapter 2, section 2.4,“Binders”. There are many commercial sources for these materials. Thesematerials are typically easy to remove via dissolution or thermaldecomposition via pyrolysis or combustion. Thermal treatment istypically part of many manufacturing processes and thus removal of thesacrificial material may be accomplished during an existing heatingstep. For this reason, thermal decomposition via pyrolysis or combustionis a more preferred method of removal.

There are several properties that are preferred in the sacrificialmaterials. The materials are preferably capable of being coated onto asubstrate via slide coating, extrusion, knife coating, solvent coating,cast and cure, or other typical coating methods. It is preferred thatthe materials be a solid at room temperature. For thermoplasticsacrificial materials, it is preferred that a working temperature,defined as the range between the glass transition temperature (T_(g)),or the temperature range over which the material exhibits viscosityappropriate for extrusion, and the onset of thermal decomposition(T_(dec)) is large enough, such as at least 50-100° C., to allow it tobe extruded as part of a multilayer film. Polymers used to make films inextrusion operations generally should exhibit complex viscosity in therange between 10³ and 10⁴ Poise at a shear rate of 100/sec. Typically,these polymers have a high enough molecular weight to provide anintrinsic viscosity of 0.4 dl/g as measured per ASTM D4603-91 using a60/40 mixture of phenol/o-dichlorobenzene as the solvent at 30° C.

Materials that thermally decompose with low ash or low total residue arepreferred over those that leave higher levels of residue. Residue leftbehind on a substrate may adversely impact electrical and/or opticalproperties such as the conductivity, transparency or color of the finalproduct. Since it is desirable to minimize any changes to theseproperties in the final product, residue levels of less than 1000 ppmare preferred. Residues levels of less than 500 ppm are more preferredand residue level below 50 ppm are most preferred. The term “cleanlybaked out” means that the sacrificial layer can be removed by pyrolysis,combustion, sublimation, or vaporization without leaving a substantialamount of residue material such as ash. Examples of preferred residuelevels are provided above, although different residue levels can be useddepending upon a particular application.

Sacrificial Adhesive Layer

The sacrificial adhesive layer can be implemented with any materialenhancing adhesion of the transfer film to the receptor substratewithout substantially adversely affecting the performance of thetransfer film. This layer can also be described as an adhesion promotinglayer. The sacrificial adhesive layer appears to facilitate the finalpermanent bond between the receptor substrate and the baked-outthermally stable structure. The sacrificial adhesive layer is capable ofbeing cleanly baked out using the methods described herein.

Useful sacrificial adhesives or adhesion promoting materials includephotoresists (positive and negative), self-assembled monolayers, silanecoupling agents, and macromolecules. In some embodiments,silsesquioxanes can function as adhesion promoting layers. Otherexemplary materials may include benzocyclobutenes, polyimides,polyamides, silicones, polysiloxanes, silicone hybrid polymers,(meth)acrylates, and other silanes or macromolecules functionalized witha wide variety of reactive groups such as epoxide, episulfide, vinyl,hydroxyl, allyloxy, (meth)acrylate, isocyanate, cyanoester, acetoxy,(meth)acrylamide, thiol, silanol, carboxylic acid, amino, vinyl ether,phenolic, aldehyde, alkyl halide, cinnamate, azide, aziridine, alkene,carbamate, imide, amide, alkyne, and any derivatives or combinations ofthese groups.Thus, embodiments of ELECTRICAL MULTILAYER LAMINATION TRANSFER FILMS aredisclosed.

All references and publications cited herein are expressly incorporatedherein by reference in their entirety into this disclosure, except tothe extent they may directly contradict this disclosure. Althoughspecific embodiments have been illustrated and described herein, it willbe appreciated by those of ordinary skill in the art that a variety ofalternate and/or equivalent implementations can be substituted for thespecific embodiments shown and described without departing from thescope of the present disclosure. This application is intended to coverany adaptations or variations of the specific embodiments discussedherein. Therefore, it is intended that this disclosure be limited onlyby the claims and the equivalents thereof. The disclosed embodiments arepresented for purposes of illustration and not limitation.

Select embodiments of the present disclosure include, but are notlimited to, the following:

In a first embodiment, the present disclosure provides a transfer filmcomprising:

a plurality of co-extensive electrical protolayers forming an electricalprotolayer stack, at least selected or each electrical protolayerindependently comprising at least 25 wt % sacrificial material and athermally stable material and having a uniform thickness of less than 25micrometers.

In a second embodiment, the present disclosure provides transfer filmcomprising a plurality of co-extensive electrical protolayers forming anelectrical protolayer stack, at least selected or each protolayerindependently exhibiting a complex viscosity of between 10³ and 10⁴Poise at a shear rate of 100/s when heated to a temperature between itsT_(g) and T_(dec).

In a third embodiment, the present disclosure provides a transfer filmaccording to claim 1, wherein the plurality of co-extensive electricalprotolayers are interdigitated.

In a fourth embodiment, the present disclosure provides a transfer filmaccording to claim 2, wherein the plurality of co-extensive electricalprotolayers are interdigitated.

In a fifth embodiment, the present disclosure provides a transfer filmaccording to any one of the first through fourth embodiments, wherein atleast selected electrical protolayers are electrically conductive.

In a sixth embodiment, the present disclosure provides a transfer filmaccording to any one of the first through fifth embodiments, whereineach or at least selected electrical protolayers comprise less than 75wt % inorganic nanomaterials.

In a seventh embodiment, the present disclosure provides a transfer filmaccording to any one of the first through sixth embodiments furthercomprising a polymeric support layer having a releasable surface, thereleasable surface contacting the electrical protolayer stack.

In an eighth embodiment, the present disclosure provides a transfer filmaccording to any one of the first through seventh embodiments, whereinthe electrical protolayer stack comprises an electrode protolayercomprising electrically conductive material and a dielectric protolayercomprising electrically insulating material.

In a ninth embodiment, the present disclosure provides a transfer filmaccording to any one of the first through eighth embodiments, whereinthe electrical protolayer stack comprises a negative electrodeprotolayer comprising negative electrode material, a positive electrodeprotolayer comprising positive electrode material and an electrolyteprotolayer comprising electrolyte material and the electrolyteprotolayer is disposed between the negative electrode protolayer and thepositive electrode protolayer.

In a tenth embodiment, the present disclosure provides a transfer filmaccording to any one of the first through ninth embodiments, wherein theelectrical protolayer stack comprises a plurality of electrochromicprotolayers comprising electrochromic material and an optionalelectrolyte protolayer comprising an electrolyte material.

In an eleventh embodiment, the present disclosure provides a transferfilm according to the tenth embodiment, wherein the electrochromicmaterial comprises at least one of, tungsten oxide, iridium oxide,nickel oxide, hydrous nickel oxide, molybdenum oxide, vanadium oxide,niobium oxide, titanium oxide, transition metal oxides of manganese,cobalt, rhodium, and ruthenium, Prussian Blue and metal phthalocyanines.

In a twelfth embodiment, the present disclosure provides a transfer filmaccording to the tenth embodiment, wherein the electrochromic materialcomprises at least one PW₁₂O₄₀ ³⁻, SiW₁₂O₄₀ ⁴⁻, W₁₀O₃₂ ³⁻,[Eu—(H₂O)P₅W₃₀O₁₁]¹²⁻, WO₃, IrO₂, Ir(OH)₃, MoO₃, V₂O₅, Nb₂O₅, TiO₂,(Fe(III)₄[Fe(II)(CN)₆]₃, and KFe(III)Fe(II)(CN)₆).

In a thirteenth embodiment, the present disclosure provides a transferfilm according to any one of the first through twelfth embodiments,wherein at least selected electrical protolayers comprise inorganicnanomaterial having an average size of less than 1000 nm.

In a fourteenth embodiment, the present disclosure provides a transferfilm according to any one of the first through thirteenth embodiments,wherein sacrificial material comprises an organic polymer material.

In a fifteenth embodiment, the present disclosure provides a transferfilm according to any one of the first through fourteenth embodiments,wherein the sacrificial material is present in each electricalprotolayer in a range from 25 to 95 wt %.

In a sixteenth embodiment, the present disclosure provides a transferfilm according to any one of the first through fifteenth embodiments,wherein the electrical protolayer stack comprises at least 10 electricalprotolayers.

In a seventeenth embodiment, the present disclosure provides a transferfilm according to any one of the first through sixteenth embodiments,wherein at least selected electrical protolayers comprise inorganicnanoparticles and an organometallic polymer or coordination compound.

In an eighteenth embodiment, the present disclosure provides a methodcomprising:

laminating a transfer film according to any of the first throughseventeenth, thirty-third and thirty-fourth embodiments, to a receptorsubstrate; and

baking out sacrificial material to form an electrical stack.

In an nineteenth embodiment, the present disclosure provides a methodaccording to the eighteenth embodiment, wherein the baking out stepforms at least one porous layer and further comprising infusing theporous layer with an electrically active liquid.

In a twentieth embodiment, the present disclosure provides a methodaccording to the nineteenth embodiment, wherein the electrically activeliquid comprises an electrolyte, an electrochromic dye, a liquidcrystal, an ionic species or a ferrofluid.

In a twenty-first embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twentieth embodiments,wherein the receptor substrate comprises glass, quartz or sapphire.

In a twenty-second embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twentieth embodiments,wherein the receptor substrate comprises an electrically conductivelayer.

In a twenty-third embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twentieth embodiments,wherein the electrical stack forms at least a portion of anelectrochromic device.

In a twenty-fourth embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twentieth embodiments,wherein the electrical stack forms at least a portion of a battery.

In a twenty-fifth embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twentieth embodiments,wherein the electrical stack forms at least a portion of a capacitor.

In a twenty-sixth embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twenty-fifth embodiments,wherein the receptor substrate comprises a bottom electrode.

In a twenty-seventh embodiment, the present disclosure provides a methodaccording to any one of the eighteenth through twenty-sixth embodimentsfurther comprising applying a top electrode on the electrical stack.

In a twenty-eighth embodiment, the present disclosure provides a methodof forming a transfer film comprising forming a plurality of electricalprotolayers to form an electrical protolayer stack, each protolayerindependently comprising a sacrificial material and a thermally stablematerial and having a uniform thickness of less than 25 micrometers.

In a twenty-ninth embodiment, the present disclosure provides a methodof forming a transfer film according to the twenty-eighth embodiment,wherein the electrical protolayers are interdigitated.

In a thirtieth embodiment, the present disclosure provides a method offorming a transfer film according to the twenty-eighth or twenty-ninthembodiments, wherein forming a plurality of electrical protolayerscomprises coextruding the plurality of electrical protolayers.

In a thirty-first embodiment, the present disclosure provides a methodof forming a transfer film according to any one of the twenty-eighththrough thirtieth embodiments, wherein each electrical protolayer of theelectrical protolayer stack independently exhibits a complex viscosityof between 10³ and 10⁴ Poise at a shear rate of 100/s when heated to atemperature between its T_(g) and T_(dec).

In a thirty-second embodiment, the present disclosure provides a methodof forming a transfer film according to any one of the twenty-eighththrough thirty-first embodiments, wherein the electrical protolayerstack is formed on a releasable surface of a polymeric supportsubstrate.

In a thirty-third embodiment, the present disclosure provides a transferfilm according to any one of the first through seventeenth embodiments,wherein the protolayer stack comprises a first plurality of electricalprotolayers interdigitated with a second plurality of electricalprotolayers.

In a thirty-fourth embodiment, the present disclosure provides atransfer film according to any one of the first through seventeenth andthirty-third embodiments, wherein each electrical protolayer of theelectrical protolayer stack independently exhibits a complex viscosityof between 10³ and 10⁴ Poise at a shear rate of 100/s when heated to atemperature between its T_(g) and T_(dec).

Examples

Electrical multilayer lamination transfer films were prepared usingcoating methods. These films were transferred to receptor substrates andsome were additionally processed into electrochromic devices.

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, etc. in the examples and the rest of thespecification are by weight, unless noted otherwise. Solvents and otherreagents used were obtained from Sigma-Aldrich Chemical Company, St.Louis, Mo. unless otherwise noted.

Material List Materials Abbreviation Description C1 Vanadyltriisopropoxide (VO(OiPr)₃) available from Sigma-Aldrich, Milwaukee,Wisconsin C2 Niobium 2-ethylhexanoate (Nb(C₇H₁₅CO₂)₄) available fromStrem Chemicals, Newburyport, Massachusetts. C3 Niobium ethoxide(Nb(OEt)₅) available from Sigma-Aldrich. C4 Tungsten ethoxide (W(OEt)₅)available from Gelest, Morrisville, Pennsylvania. C5 Tin(II)acetylacetonate (Sn(acac)₂) available from Sigma-Aldrich. M1 Monomer,Beta-carboxyethyl acrylate (CEA) (HO₂CCH₂CH₂OCOCH═CH₂) available fromSigma-Aldrich. M2 Monomer, Acetoacetoxyethyl methacrylate (ACACEMA)(CH₃COCH₂CO₂CH₂CH₂OCOC(CH₃)═CH₂) available from Pfaltz & Bauer,Waterbury, Connecticut. C6 Molybdenum 2-ethylhexanoate (Mo(C₇H₁₅CO₂)₄)available from American Elements, Los Angeles, California. C7Acetylacetone (CH₃COCH₂COCH₃) available from Alfa Aesar, Ward Hill,Massachusetts. C8 Zirconium acetylacetonate (Zr(acac)₄) fromSigma-Aldrich. C9 Molybdenum (V) chloride (MoCl₅) from Sigma-Aldrich.PH1 Photoinitiator, available under the trade designation “IRGACURE4265” from BASF, Florham Park, New Jersey. B1 Binder, Poly(propylenecarbonate) available under the trade designation “QPAC 40” from EmpowerMaterials, New Castle, Delaware. COP1 PMMA copolymer solution, 75 wt %methyl methacrylate, 25 wt % ethyl acrylate, 20% wt. solution in2-butanone, available under the trade designation “PRD510-A” fromAltuglas International (North America), Bristol, Pennsylvania. M3Monomer, ethoxylated bisphenol A diacrylate, available under the tradedesignation “SR540” from Sartomer, Warrington, Pennsylvania. PH2Photoinitiator, available under the trade designation “IRGACURE 1173”from BASF. PH3 Photoinitiator, available under the trade designation“IRGACURE TPO” from BASF. NP1 Nanoparticles, 45.2 wt % solids dispersionof 10 nm zirconia particles prepared as described in U.S. Pat. No.7,241,437, Example 4. U.S. Pat. No. 7,241,437 is incorporated herein byreference in its entirety. I1 Polymerization Inhibitor, available underthe trade designation “PROSTAB 5198” from BASF, prepared as a 5 wt. %aqueous solution. A1 PEG350 succinate ester acid prepared frompolyethylene glycol 350 and succinic anhydride using methods describedin U.S. Pat. No. 8,282,863, Example 1. U.S. Pat. No. 8,282,863 isincorporated herein by reference in its entirety. PSA1Pressure-sensitive adhesive solution prepared by diluting a 93:7 (w/w)isooctyl acrylate:acrylic acid copolymer (monomers available from SigmaAldrich); copolymer prepared using methods described in U.S. Pat. No.4,737,577, Example 1, diluted to 5 wt % solids in 1:1 (w/w) ethylacetate:heptane. U.S. Pat. No. 4,737,577 is incorporated herein byreference in its entirety. E1 Electrolyte, Lithiumbis(trifluoromethanesulfonimide) available under the trade designation“HQ-115” from 3M Company, St. Paul, MN. S1 Surfactant, available underthe trade designation “TEGO Rad 2250” from Evonik Industries AG, Essen,Germany.

Preparation of Release Film

The release substrate used in the Examples was a 2 mil PET film coatedwith 6 micron thick PMMA copolymer release layer (COP1 solution) using aroll-to-roll web coating process. The coating solution was dried toremove solvent. The PMMA copolymer release layer was further treatedwith a solvent barrier by applying a solution of M3 50 wt %, PH2 0.5 wt% and PH3 0.1 wt % in 80:20 (w/w) isopropyl alcohol:2-butanone using aroll-to-roll coating process. The coating solution was supplied at arate of 1 cc/min to a 10.2 cm wide slot type coating die, and applied tothe above PMMA-coated PET film substrate moving at a web speed of 305cm/min to give a wet film thickness of approximately 6.5 microns.Impinging air flow was applied immediately onto the film after coatingto remove the bulk of the solvent. The coated web travelled a 3 m spanat ambient temperature, then into two 1.5 m drying zones set at 77° C.Finally, the dried coating entered a UV curing chamber equipped with aFusion System Model I300P H-bulb. The chamber was purged by a gas streampre-mixed with nitrogen to maintain an oxygen level under 50 ppm. Thisresulted in the Release Film.

Example 1—Preparation, Transfer, and Baking of Three-Layer VanadiumOxide/Zirconium Oxide/Tungsten Oxide Precursor Transfer Film Preparationof Tungsten Oxide Precursor Resin Solution

Equal parts by weight of C4 and M1 were mixed in a screw-top vial andshaken to give a clear, single-phase light yellow liquid. In an amberglass screw-top jar, a clear, light yellow coating solution was preparedthat consisted of 20 wt % of the above liquid and 0.4 wt % PH1 in 90:102-butanone: 1-methoxy-2-propanol, the Tungsten Oxide Precursor ResinSolution.

Preparation of Zirconium Oxide Precursor Resin Solution

A 500 ml 3-neck round bottom flask was charged with 100.0 grams of NP1.Next, 200.0 grams 1-methoxy-2-propanol (Alfa Aesar, Ward Hill, Mass.)were added to the batch. The batch was held for approximately 15 minutesat room temperature with mixing. Next, 0.38 grams of I1, 7.32 grams ofA1 and 48.0 grams of M3 were added to the batch with stirring. The batchwas placed on a rotary evaporator and the solvent was removed withvacuum and heating to 60° C. The final mixture was a very fluid, nearlyclear dispersion, isolated in a yield of 102.3 grams.

In an amber glass screw-top jar, a coating solution was prepared thatconsisted of 3.33 wt % the above resin, 1.67 wt % C8, and 0.1 wt % PH1in 90:10 (w/w) 2-butanone:1-methoxy-2-propanol, the Zirconium OxidePrecursor Resin Solution.

Preparation of Vanadium Oxide Precursor Resin Solution

One part by weight C1 and two parts by weight M2 were mixed in a glassscrew-top vial and shaken to give a clear, single-phase dark red liquid.In an amber glass screw-top jar, a clear red coating solution wasprepared that consisted of 10 wt % the above liquid and 0.2 wt % PH1 in90:10 (w/w) 2-butanone: 1-methoxy-2-propanol, the Vanadium OxidePrecursor Resin Solution.

Preparation, Transfer, and Baking of Three-Layer Transfer Film

A sample of the Release Film prepared above was coated with thefollowing three layers in succession:

1) Tungsten Oxide Precursor Resin Solution using a #9 wire-wound rod (RDSpecialties, Webster, N.Y.);

2) Zirconium Oxide Precursor Resin Solution using a #6 wire-wound rod;

3) Vanadium Oxide Precursor Resin Solution using a #6 wire-wound rod.

All coating solutions were filtered through 1 micron filter cartridgesjust prior to coating. Each layer was dried in a forced-air oven at 70°C. for 2 min and cured by two passes through a Fusion UV Systems, Inc.Lighthammer UV processor equipped with a D type mercury lamp operated at100% power and using a conveyor speed of 30 ft/min (9.1 m/min) undernitrogen inerting, before application of the next layer. This produced aThree-Layer Precursor Film, i.e. a protolayer stack having three layers.

A receptor substrate, consisting of a glass slide coated with indium tinoxide (50 ohm/sq, Delta Technologies, Loveland, Colo.), was treated withPSA1 by spin coating at 1000 rpm. The sample was placed in a forced-airoven at 120° C. for 5 min to dry the adhesive. The Three-Layer PrecursorFilm from above was laminated to the adhesive using an adhesive rollerunder hand pressure, and the laminate was heated in a forced-air oven at120° C. for 3 min. After cooling, the Release Film was carefullyremoved, leaving the three-layer precursor layers behind on the glassslide. The glass slide was placed in a THERMOLYNE (available from ThermoScientific, Grand Island, N.Y.) programmable ceramic oven and heatedusing a 2° C./min ramp to 300° C., held at that temperature for 2 hr,ramped to 350° C. at 2° C./min, held at that temperature for 2 hr,ramped to 425° C. at 2° C./min, and held at that temperature for 2 hr.It was then allowed to cool to room temperature. The sample wassubjected to cross-sectional scanning electron microscopy (SEM) imagingfor analysis of the resulting baked three-layer transferred stack. Theimage showed, in order beginning at the bottom of the image, the glassreceptor substrate; ITO layer; vanadium oxide (approximately 137 nmthick); zirconium oxide (approximately 146 nm thick); and tungsten oxide(approximately 128 nm thick), with the total stack thicknessapproximately 411 nm.

Example 2—Preparation, Transfer, and Baking of Three-Layer TungstenOxide/Zirconium Oxide/Vanadium Oxide Precursor Transfer Film

The same Release Film substrate, metal oxide resin coating solutions,and methods described in Example 1 were used to prepare a three-layertungsten oxide/zirconium oxide/vanadium oxide transfer film. All coatingsolutions were filtered through 1 micron filter cartridges just prior tocoating. A sample of the Release Film prepared above was coated with thefollowing three layers in succession:

1) Vanadium Oxide Precursor Resin Solution using a #9 wire-wound rod (RDSpecialties, Webster, N.Y.);

2) Zirconium Oxide Precursor Resin Solution using a #8 wire-wound rod;

3) Tungsten Oxide Precursor Resin Solution using a #9 wire-wound rod.

Each layer was dried in a forced-air oven at 70° C. for 2 min and curedby two passes through a Fusion UV Systems, Inc. Lighthammer UV processorequipped with a D type mercury lamp operated at 100% power and using aconveyor speed of 30 ft/min (9.1 m/min) under nitrogen inerting, beforeapplication of the next layer. This produced a Three-Layer PrecursorFilm, i.e. a protolayer stack having three layers.

A receptor substrate consisting of a glass slide coated with indium tinoxide (50 ohm/sq, Delta Technologies, Loveland, Colo.) was treated withPSA1 by spin coating at 500 rpm for 5 sec, then 1000 rpm for 15 sec. Thesample was placed in a forced-air oven at 120° C. for 5 min to dry theadhesive. The Three-Layer Precursor Film from above was laminated to theadhesive using an adhesive roller under hand pressure, and the laminatewas heated in a forced-air oven at 120° C. for 3 min. After cooling, theRelease Film was carefully removed, leaving the three-layer precursorlayers behind on the glass slide. The glass slide was then placed in aTHERMOLYNE (Thermo Scientific, Grand Island, N.Y.) programmable ceramicoven and heated using a 2° C./min ramp to 300° C., held at thattemperature for 2 hr, ramped to 350° C. at 2° C./min, held at thattemperature for 2 hr, ramped to 425° C. at 2° C./min, held at thattemperature for 2 hr, and allowed to cool to room temperature. Thesample was subjected to cross-sectional SEM imaging for analysis of theresulting baked three-layer transferred stack. The image showed, inorder beginning at the bottom of the image, the glass receptorsubstrate; ITO layer; tungsten oxide (approximately 120 nm thick);zirconium oxide (approximately 86 nm thick); and vanadium oxide(approximately 94 nm thick), with a total stack thickness approximately300 nm.

The sample was immersed in a solution of 0.5 M E1 (vacuum dried at 140°C. overnight before use) in acetonitrile (Aldrich, dried over molecularsieves before use) and connected as the working electrode in anelectrochemical setup using a Bio-Logic (Knoxville, Tenn.) SP-300potentiostat equipped with a silver wire reference electrode and aplatinum mesh counter electrode. Application of −0.8 V (vs thereference) to the working electrode caused lithiation of the tungstenoxide bottom layer and formation of a pronounced blue color. Switchingthe voltage to +1.0 V vs the reference caused fading to a very lightblue, almost colorless delithiated state. The coating could be cycledmultiple times between dark and light states in this half-cellconfiguration. The sample was switched at 200 mV/sec between −0.8 V and+1.0 V vs Ag wire reference, holding for 1 min at each voltage.Reversible delithiation charge transfer was approximately 9.4 mC/cm².

Examples 3-6—Additional Resins Useful in Metal Oxide Precursor FilmsExample 3

Equal parts by weight of C2 and M1 were mixed in a glass screw-top vial.After shaking, the initially hazy mixture became a clear, light yellow,single-phase liquid with good stability to storage at room temperature.This liquid resin was diluted to 20 wt % solids in 90:10 (w/w)2-butanone: 1-methoxy-2-propanol or acetylacetone (C7) and formulatedwith photoinitiator such as PH1 to yield coating solutions forpreparation of UV-curable coatings useful in transfer filmconstructions.

Example 4

Equal parts by weight of C5 and M2 were mixed in a glass screw-top vialto give a clear single-phase orange liquid resin. This resin was dilutedto 10 wt % in 2-butanone or acetylacetone (C7) to give coating solutionsfor use in preparation of transfer films. Coatings of this resin appliedfrom 10 wt % solution in acetylacetone (C7) to glass slides by spincoating (250 to 2000 rpm) were allowed to dry in air then baked in aceramic oven at 550° C. for 1 hr to yield clear, mechanically robustfilms of tin(IV) oxide.

Example 5

Equal parts by weight of C6 and M1 were mixed in a glass screw-top vial.After shaking, a clear, very dark red single-phase liquid resin wasobtained. This resin was dissolved at 10 wt % in 2-butanone and could beformulated with photoinitiator such as PH1 to yield coating solutionsfor preparation of UV-curable coatings useful in transfer filmconstructions.

Example 6

A glass screw-top vial was charged with 0.7 g C9, 3.5 g 20 wt % solidssolution of B1 in 2-butanone, and 9.8 g of 2-butanone. The resultingmixture was shaken to yield a clear, dark red single-phase solutioncontaining 5 wt % B1 solids and 5 wt % C9. This solution was coated toyield dried layers useful in preparation of transfer film constructions.It was spin coated (1000 rpm/60 sec) on a glass slide, and the solventwas allowed to flash off at room temperature. The slide was placed in aprogrammable ceramic oven and heated using a 2° C./min ramp to 300° C.,held at that temperature for 2 hr, ramped to 350° C. at 2° C./min, heldat that temperature for 4 hr, and then allowed to cool to roomtemperature. SEM cross-sectional imaging of the resulting molybdenumoxide coating showed thickness of 120-230 nm.

Example 7—Preparation of Two- and Three-Layer Transfer Films by InlineSlot Die Coating Preparation of Vanadium Oxide Precursor Resin Solution2

One part by weight C1 and two parts by weight M2 were mixed in a glassscrew-top vial and shaken to give a clear, single-phase dark red liquid.In an amber glass screw-top jar, a clear red coating solution wasprepared that consisted of 20 wt % the above liquid and 0.4 wt % PH1 in90:10 (w/w) 2-butanone: 1-methoxy-2-propanol, the Vanadium OxidePrecursor Resin Solution 2.

Preparation of Niobium Oxide Precursor Resin Solution

One part by weight C2 and one part by weight M2 were mixed in a glassscrew-top vial and shaken to give an initially cloudy mixture whichclarified within a few seconds to a clear, light yellow, single-phaseliquid. In an amber glass screw-top jar, a coating solution was preparedthat consisted of 20 wt % the above liquid, 0.4 wt % PH1, and 0.03 wt %S1, the Niobium Oxide Precursor Resin Solution.

A sample of the Release Film prepared above was coated with solutions ofthe metal oxide precursor resins in a roll-to-roll coating process.First, the above Vanadium Oxide Precursor Resin Solution 2 was suppliedat a rate of 1 cc/min to a 10.2 cm wide slot type coating die, andapplied to the Release Film substrate moving at a web speed of 152cm/min. Impinging air flow was applied immediately onto the film aftercoating to remove the bulk of the solvent. The coated web travelled a 3m span at ambient temperature, then into two 1.5 m drying zones set at77° C. Finally, the dried coating entered a UV curing chamber equippedwith a Fusion System Model I300P H-bulb. The chamber was purged by a gasstream pre-mixed with nitrogen to maintain an oxygen level under 50 ppm.A portion of the resulting One-Layer Precursor Film was coated again,this time with the Zirconium Oxide Resin Precursor Solution of Example1, supplied at a rate of 2 cc/min to the film web moving at a web speedof 305 cm/min. Impinging air flow was applied immediately onto the filmafter coating to remove the bulk of the solvent. The coated webtravelled a 3 m span at ambient temperature, then into two 1.5 m dryingzones set at 77° C. Finally, the dried coating entered a UV curingchamber equipped with a Fusion System Model I300P H-bulb. The chamberwas purged by a gas stream pre-mixed with nitrogen to maintain an oxygenlevel under 50 ppm, producing a Two-Layer Precursor Film, i.e. aprotolayer stack having two layers. A sample of the Two-Layer TransferFilm was subjected to cross-sectional imaging analysis by SEM. The imageshowed an approximately 90 nm thick bottom layer of vanadium oxideprecursor resin and an approximately 97 nm thick top layer of zirconiumoxide precursor resin, on the release layer.

A portion of the resulting Two-Layer Precursor Film was coated again,this time with the Niobium Oxide Resin Precursor Solution, supplied at arate of 3 cc/min to the film web moving at a web speed of 305 cm/min.Impinging air flow was applied immediately onto the film after coatingto remove the bulk of the solvent. The coated web travelled a 3 m spanat ambient temperature, then into two 1.5 m drying zones set at 77° C.Finally, the dried coating entered a UV curing chamber equipped with aFusion System Model I300P H-bulb. The chamber was purged by a gas streampre-mixed with nitrogen to maintain an oxygen level under 50 ppm,producing a Three-Layer Precursor Film, i.e. a protolayer stack havingthree layers. The Three-Layer Precursor Film was subjected tocross-sectional imaging analysis by SEM. The image showed the PET filmsubstrate, the release layer with thickness approximately 12 microns,and three layer protolayer stack consisting of the vanadium oxideprecursor layer with thickness approximately 97 nm, then the zirconiumoxide precursor layer with thickness approximately 63 nm, and then theniobium oxide precursor layer with thickness approximately 290 nm. Thetotal stack thickness was approximately 450 nm.

Example 8

A glass screw-top vial was charged with 0.07 g C9, 7.0 g 20 wt % solidssolution of B1 in 2-butanone, and 6.93 g of 2-butanone. The resultingmixture was shaken to yield a clear, dark red single-phase solutioncontaining 10 wt % B1 solids and 0.5 wt % C9. The solution was allowedto stand overnight at room temperature, then coated on the Two-LayerPrecursor Film from Example 7 using a knife coater set at a gap of 40microns. The film was dried in a forced-air oven at 70° C. for 2 min,producing a Three-Layer Precursor Film, i.e. a protolayer stack havingthree layers. The sample was subjected to cross-sectional imaginganalysis by SEM. The image showed the molybdenum oxide precursor layerwith thickness approximately 1 micron on the vanadium oxide andzirconium oxide precursor layers present on the original Two-LayerPrecursor Film.

What is claimed is:
 1. A transfer film comprising: a plurality ofco-extensive electrical protolayers forming an electrical protolayerstack, at least selected or each electrical protolayer independentlycomprising at least 25 wt % sacrificial material and a thermally stablematerial and having a uniform thickness of less than 25 micrometers. 2.A transfer film comprising: a plurality of co-extensive electricalprotolayers forming an electrical protolayer stack, at least selected oreach protolayer independently exhibiting a complex viscosity of between10³ and 10⁴ Poise at a shear rate of 100/s when heated to a temperaturebetween its T_(g) and T_(dec).
 3. A transfer film according to claim 1,wherein the plurality of co-extensive electrical protolayers areinterdigitated.
 4. A transfer film according to claim 2, wherein theplurality of co-extensive electrical protolayers are interdigitated. 5.A transfer film according to claim 1, wherein at least selectedelectrical protolayers are electrically conductive.
 6. The transfer filmaccording to claim 1, wherein each or at least selected electricalprotolayers comprise less than 75 wt % inorganic nanomaterials.
 7. Atransfer film according to claim 1 further comprising a polymericsupport layer having a releasable surface, the releasable surfacecontacting the electrical protolayer stack.
 8. A transfer film accordingto claim 1, wherein the electrical protolayer stack comprises anelectrode protolayer comprising electrically conductive material and adielectric protolayer comprising electrically insulating material.
 9. Atransfer film according to claim 1, wherein the electrical protolayerstack comprises a negative electrode protolayer comprising negativeelectrode material, a positive electrode protolayer comprising positiveelectrode material and an electrolyte protolayer comprising electrolytematerial and the electrolyte protolayer is disposed between the negativeelectrode protolayer and the positive electrode protolayer.
 10. Atransfer film according to claim 1, wherein the electrical protolayerstack comprises a plurality of electrochromic protolayers comprisingelectrochromic material and an optional electrolyte protolayercomprising an electrolyte material.
 11. The transfer film according toclaim 10, wherein the electrochromic material comprises at least one of,tungsten oxide, iridium oxide, nickel oxide, hydrous nickel oxide,molybdenum oxide, vanadium oxide, niobium oxide, titanium oxide,transition metal oxides of manganese, cobalt, rhodium, and ruthenium,Prussian Blue and metal phthalocyanines.
 12. The transfer film accordingto claim 10, wherein the electrochromic material comprises at least onePW₁₂O₄₀ ³⁻, SiW₁₂O₄₀ ⁴⁻, W₁₀O₃₂ ³⁻, [Eu—(H₂O)P₅W₃₀O₁₁]¹²⁻, WO₃, IrO₂,Ir(OH)₃, MoO₃, V₂O₅, Nb₂O₅, TiO₂, (Fe(III)₄[Fe(II)(CN)₆]₃, andKFe(III)Fe(II)(CN)₆).
 13. A transfer film according to claim 1, whereinat least selected electrical protolayers comprise inorganic nanomaterialhaving an average size of less than 1000 nm.
 14. A transfer filmaccording to claim 1, wherein sacrificial material comprises an organicpolymer material.
 15. A transfer film according to claim 1, wherein thesacrificial material is present in each electrical protolayer in a rangefrom 25 to 95 wt %.
 16. A transfer film according to claim 1, whereinthe electrical protolayer stack comprises at least 10 electricalprotolayers.
 17. A transfer film according to claim 1, wherein at leastselected electrical protolayers comprise inorganic nanoparticles and anorganometallic polymer or coordination compound.
 18. A method,comprising: laminating the transfer film according to claim 1 to areceptor substrate; and baking out sacrificial material to form anelectrical stack.
 19. A method according to claim 18, wherein the bakingout step forms at least one porous layer and further comprising infusingthe porous layer with an electrically active liquid.
 20. A methodaccording to claim 19, wherein the electrically active liquid comprisesan electrolyte, an electrochromic dye, a liquid crystal, an ionicspecies or a ferrofluid.
 21. A method according to claim 18, wherein thereceptor substrate comprises glass, quartz or sapphire.
 22. A methodaccording to claim 18, wherein the receptor substrate comprises anelectrically conductive layer.
 23. A method according to claim 18,wherein the electrical stack forms at least a portion of anelectrochromic device.
 24. A method according to claim 18, wherein theelectrical stack forms at least a portion of a battery.
 25. A methodaccording to claim 18, wherein the electrical stack forms at least aportion of a capacitor.
 26. A method according to any of claim 18,wherein the receptor substrate comprises a bottom electrode.
 27. Amethod according to any of claim 18 further comprising applying a topelectrode on the electrical stack.
 28. A method of forming a transferfilm, comprising: forming a plurality of electrical protolayers to forman electrical protolayer stack, each protolayer independently comprisinga sacrificial material and a thermally stable material and having auniform thickness of less than 25 micrometers.
 29. A method according toclaim 28, wherein the electrical protolayers are interdigitated.
 30. Amethod according to claim 28, wherein forming a plurality of electricalprotolayers comprises coextruding the plurality of electricalprotolayers.
 31. A method according to claim 28, wherein each electricalprotolayer of the electrical protolayer stack independently exhibits acomplex viscosity of between 10³ and 10⁴ Poise at a shear rate of 100/swhen heated to a temperature between its T_(g) and T_(dec).
 32. A methodaccording to any of claim 28, wherein the electrical protolayer stack isformed on a releasable surface of a polymeric support substrate.